(2S)-ethyl 3-(cyclopenten-1'-yl)-2-(trifluoromethyl)-2-hydroxypropanoate

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (2S)-ethyl 3-(cyclopenten-1'-yl)-2-(trifluoromethyl)-2-hydroxypropanoate
• 英文别名: (S)-ethyl 2-(cyclopentenylmethyl)-3,3,3-trifluoro-2-hydroxypropanoate；ethyl 3-(cyclopenten-1′-yl)-2-(trifluoromethyl)-2-hydroxypropanoate；ethyl (2S)-2-(cyclopenten-1-ylmethyl)-3,3,3-trifluoro-2-hydroxypropanoate
• 化学式: C₁₁H₁₅F₃O₃
• 分子量: 252.234
• InChiKey: MXOBHKBHJAEDJP-JTQLQIEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  亚甲基环戊烷 、 3,3,3-三氟丙酮酸乙酯 在 silver hexafluoroantimonate 、 二氯[2，2’-二(二苯基磷)-1，1’-联萘]钯(II) 作用下， 反应 0.5h， 以82%的产率得到(2S)-ethyl 3-(cyclopenten-1'-yl)-2-(trifluoromethyl)-2-hydroxypropanoate
  参考文献：
  名称：

  Tandem ionic liquid antimicrobial toxicity and asymmetric catalysis study: carbonyl-ene reactions with trifluoropyruvate

  摘要：

  在低抗菌毒性的C2取代咪唑鎓离子液体（ILs）中，三氟丙酮酸与五种烯烃的非对称羰基-烯反应在[Pd{(R)-BINAP}](SbF6)2催化下，实现了良好的产率和立体选择性（最高达96%产率和96% ee）。在初步的IL筛选后，毒性数据被纳入反应优化的选择标准。固定在IL中的Pd(II)催化剂可回收并重复使用多达7次，且产率和ee均无下降。一种制备的IL被确定具有高抗菌毒性，因此被赋予低优先级用于未来的应用。

  DOI：

  10.1039/c3gc40875b

文献信息

• Enantioselective catalysis of carbonyl-ene and Friedel–Crafts reactions with trifluoropyruvate by ‘naked’ palladium(II) complexes with SEGPHOS ligands
  作者：Koichi Mikami、Kohsuke Aikawa、Satoshi Kainuma、Yuji Kawakami、Takao Saito、Noboru Sayo、Hidenori Kumobayashi

  DOI：10.1016/j.tetasy.2004.10.022

  日期：2004.12

  enantioselectivity not only in carbonyl-ene but also in Friedel–Crafts reactions stem from the effective shielding with diphenyl groups on phosphines caused by the narrow dihedral angle of metal complexes with SEGPHOS.

  手性双阳离子SEGPHOS -钯（II）复合物提供了高的化学产率，（É）α-烯烃的选择性，抗-diastereoselectivity，高对映选择性沿即使反应性较低的单-和在这少得多的反应性酮烯1,2-二取代的烯烃反应。对映体的高选择性不仅在羰基烯中，而且在Friedel-Crafts反应中，都归因于与SEGPHOS金属配合物的窄二面角导致的膦上二苯基的有效屏蔽。
• Asymmetric Platinum Group Metal-Catalyzed Carbonyl-Ene Reactions:  Carbon−Carbon Bond Formation versus Isomerization
  作者：Simon Doherty、Julian G. Knight、Catherine H. Smyth、Ross W. Harrington、William Clegg

  DOI：10.1021/jo062023n

  日期：2006.12.1

  comparative study of the carbonyl-ene reaction between a range of 1,1‘-disubstituted or trisubstituted alkenes and ethyl trifluoropyruvate catalyzed by Lewis acid−platinum group metal complexes of the type [M(R)-BINAP}]2+ (M = Pt, Pd, Ni; BINAP is 2,2‘-bis(diphenylphosphino)-1,1‘-binaphthyl) revealed subtle but significant differences in their reactivity. For instance, the palladium-based Lewis acid [Pd(R)-BINAP}]2+

  之间的范围内的羰基-烯反应的比较研究1,1'-二取代或三取代烯烃和乙基三氟丙酮催化由类型的路易斯酸-铂族金属配合物[M （[R）-BINAP}] 2+（ M ＝ Pt，Pd，Ni； BINAP为2，2′-双（二苯基膦基）-1，1′-联萘基）显示出微妙但显着的反应性差异。例如，基于钯的路易斯酸[Pd （R）-BINAP}] 2+催化亚甲基环烷烃之间的烯反应，从而以良好的收率和优异的非对映和对映选择性提供了预期的α-羟基酯。相反，在相同条件下，相应的[M （R）-BINAP}] 2+（M = Pt，Ni）催化亚甲基环烷烃的异构化以及亚甲基环烷烃和1-甲基环烯烃的混合物以相似的速率进行烯反应，从而以高区域选择性，良好的非对映选择性和优异的优异性能提供了一系列的α-羟基酯。对映选择性。此外，[Pt （R）-BINAP}] 2+它还催化烯产物的后反应异构化以及连续的烯反应，得到双羰基烯产物。
• Asymmetric catalysis of ene reactions with trifluoropyruvate catalyzed by dicationic palladium(II) complexes
  作者：Kohsuke Aikawa、Satoshi Kainuma、Manabu Hatano、Koichi Mikami

  DOI：10.1016/j.tetlet.2003.10.137

  日期：2004.1

  Chiral dicationic SEGPHOS-Pd(II) complex achieves a high chemical yield, (E)-olefin selectivity, anti-diastereoselectivity, along with high enantioselectivity even with less reactive mono- and 1,2-disubstituted olefins in this much less reactive ketoneene reactions. The high levels of enantio selectivity stem from the effective shielding with diphenyl groups on phosphines caused by the narrow dihedral angle of metal complexes with SEGPHOS. (C) 2003 Elsevier Ltd. All rights reserved.
• Triaryl-Like MONO-, BIS-, and TRISKITPHOS Phosphines: Synthesis, Solution NMR Studies, and a Comparison in Gold-Catalyzed Carbon–Heteroatom Bond Forming 5-<i>exo</i>-dig and 6-<i>endo</i>-dig Cyclizations
  作者：Simon Doherty、Julian G. Knight、Daniel O. Perry、Nicholas A. B. Ward、Dror M. Bittner、William McFarlane、Corinne Wills、Michael R. Probert

  DOI：10.1021/acs.organomet.6b00146

  日期：2016.5.9

  A homologous series of triaryl-like KITPHOS-type monophosphines containing one, two, or three bulky 12-phenyl-9,10-dihydro-9,10-ethenoanthracene (KITPHOS) units have been developed, and the influence of increasing steric bulk on their efficacy as ligands in gold(I)-catalyzed carbon-heteroatom bond-forming cyclizations has been investigated. Detailed solution NMR studies on Ph-TRISKITPHOS, its oxide, and the corresponding gold(I) chloride adduct identified a conformational exchange process involving a concerted librational motion of the individual anthracene-derived organic substituents about their P-C bonds. The cessation of this motion at reduced temperatures lowers the molecular symmetry such that the two C6H4 rings in each of the KITPHOS units become inequivalent; a lower energy process involving restricted rotation of the biaryl-like phenyl ring has also been identified. Electrophilic gold(I) complexes of these triaryl-like KITPHOS monophosphines catalyze the 5-exo-dig cycloisomerization of propargyl amides to afford the corresponding methylene oxazolines, which were used in a subsequent tandem carbonyl-ene reaction to afford functionalized 2 -substituted oxazolines. A comparative survey revealed that catalyst efficiency for cycloisomerization decreases in the order MONOKITPHOS = BISKITPHOS > PPh3 > TRISKITPHOS. The optimum system also catalyzes the selective 6-endo-dig cyclization of 2-alkynylbenzyl alcohols, 2-alkynylbenzoic acid, and 2-phenylethynyl benzamides; gratifyingly, in several cases the yields obtained are markedly higher and/or reaction times significantly shorter than those previously reported for related gold catalysts. Moreover, these are the first examples of gold(I)-catalyzed 6-endo-dig cycloisomerizations involving 2-phenylethynyl benzamides and, reassuringly, the optimum gold(I)/MONOKITPHOS systems either rivaled or outperformed existing silver or palladium based catalysts. The steric parameters of this homologous series of phosphines have been quantified and compared with selected triarylphosphines using a combination of Solid -G calculations, to determine the percentage of the metal coordination sphere shielded by the phosphine (the G parameter), and Salerno molecular buried volume calculations (SambVca) to determine the percent buried volume (%V-bur); the corresponding Tolman cone angles have also been determined from correlations.
• Tandem ionic liquid antimicrobial toxicity and asymmetric catalysis study: carbonyl-ene reactions with trifluoropyruvate
  作者：Rohitkumar G. Gore、Thi-Kim-Thu Truong、Milan Pour、Lauren Myles、Stephen J. Connon、Nicholas Gathergood

  DOI：10.1039/c3gc40875b

  日期：——

  The asymmetric carbonyl-ene reaction of trifluoropyruvate with five alkenes catalysed by [Pd(R)-BINAP}](SbF6)2 were carried out in good yields and enantioselectivities (up to 96% yield and 96% ee) in low antimicrobial toxicity C2-substituted imidazolium ionic liquids (ILs). Toxicity data was included in the selection criteria for reaction optimisation after a preliminary IL screen. The Pd(II) catalyst immobilised in an IL was recycled and reused up to 7 times without decrease of either yield or ee. One IL prepared, which was determined to be of high antimicrobial toxicity was assigned a low priority for future applications.

  在低抗菌毒性的C2取代咪唑鎓离子液体（ILs）中，三氟丙酮酸与五种烯烃的非对称羰基-烯反应在[Pd(R)-BINAP}](SbF6)2催化下，实现了良好的产率和立体选择性（最高达96%产率和96% ee）。在初步的IL筛选后，毒性数据被纳入反应优化的选择标准。固定在IL中的Pd(II)催化剂可回收并重复使用多达7次，且产率和ee均无下降。一种制备的IL被确定具有高抗菌毒性，因此被赋予低优先级用于未来的应用。